4-Butyl-3,4,5-trimethylcyclohexa-25-dienone

ABSTRACT

Processes and compositions are described for use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma; tobacco flavor and aroma; perfume and perfumed article aroma augmenting, enhancing and imparting compositions; and as foodstuff, chewing gum, toothpaste, medicinal product, tobacco, perfume and perfumed article aroma imparting materials of one or more cyclohexadiene derivatives having the generic formula:   &lt;IMAGE&gt; wherein R is one of C1-C5 alkyl, R1 is methyl when R2 is hydrogen, and R1 is hydrogen when R2 is methyl, produced by one of the following processes:

This is a divisional of application Ser. No. 860,123, filed on Dec. 13,1977, now U.S. Pat. No. 4,130,508, issued on 12/19/78, which, in turn,is a divisional of Ser. No. 774,058, filed on Mar. 3, 1977, now U.S.Pat. No. 4,076,854, issued on Feb. 28, 1978.

BACKGROUND OF THE INVENTION

The present invention relates to cyclohexadiene derivatives having theformula: ##STR3## wherein R is one of C₁ -C₅ alkyl, R₁ is methyl when R₂is hydrogen, and R₁ is hydrogen when R₂ is methyl, produced by theprocesses of our invention and novel compositions using one or more ofsuch cyclohexadiene derivatives to augment or enhance the flavor and/oraroma of consumable materials or impart flavor and/or aroma toconsumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply, and to provide more uniform properties in the finishedproduct.

Sweet, hay-like, heliotropine-like, black pepper-like, woody,tobacco-like and "Oriental" aroma characteristics with sweet, hay-like,heliotropine-like, black pepper-like, woody, tobacco, "Oriental" flavorcharacteristics are particularly desirable for many uses in foodstuffflavorings, chewing gum flavors, toothpaste flavors, and medicinalproduct flavors.

Warm, sweet, slightly minty, woody, natural green, herbaceous,Jasmine-like, fruity aromas are desirable in several types of perfumecompositions, perfumed articles, and colognes.

"Dry black tobacco-like" notes, spicey notes, celery-like notes, blackpepper-like notes, sweet notes and Virginia tobacco-like notes prior toand on smoking in both the main stream and side stream, are desirable intobaccos and tobacco flavors.

In the paper by Demole and Enggist, Helv. Chim. Acta. 57(Fasc.7):2087-2091 (1974), compounds having the following structures have beenfound to be present in Burley tobacco flavor: ##STR4## None of thecompounds of Demole and Enggist have properties bearing any relationshipto the properties of the cyclohexadiene derivatives of the instantapplication.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents the NMR spectrum for the compound2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one, produced according toExample II.

FIG. 2 represents the IR spectrum for the compound2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one, produced according toExample II.

FIG. 3 represents the NMR spectrum for the compound4-hydroxy-2,4,6,6-tetramethylcyclohexa-2-en-1-one, produced according toExample II.

FIG. 4 represents the IR spectrum for the compound4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one, produced according toExample II.

FIG. 5 represents the NMR spectrum for the compound4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one, produced accordingto Example IV.

FIG. 6 represents the IR spectrum for the compound4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one, produced accordingto Example IV.

FIG. 7 represents the NMR spectrum for the compound4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one, produced according toExample V.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having sweet, hay-like, heliotropine-like, blackpepper-like, woody, tobacco-like and "Oriental" aroma characteristicswith sweet, hay-like, heliotropine-like, black pepper-like, woody,tobacco, "Oriental" flavor characteristics; novel perfume compositions,colognes and perfumed articles having warm, sweet, slightly minty,woody, natural green, herbaceous, Jasmine-like, fruity aromas; and noveltobacco and tobacco flavor compositions having "dry black tobacco-like"notes, spicey notes, celery-like notes, black pepper-like notes, sweetnotes and Virginia tobacco-like notes prior to and on smoking in boththe main stream and side stream, may be provided by the utilization ofcyclohexadiene derivatives having the formula: ##STR5## wherein R is oneof C₁ -C₅ alkyl, R₁ is methyl when R₂ is hydrogen, and R₁ is hydrogenwhen R₂ is methyl, in foodstuffs, chewing gums, toothpastes, medicinalproduct flavors, perfumes, colognes, perfumed articles, tobaccos andtobacco flavors.

The cyclohexadiene derivatives useful as indicated herein may beproduced according to one of the following processes:

(1) Reacting an alkyl-trimethylcyclohexa-1,3-diene with oxygen in thepresence of light, an ultraviolet sensitizer and a basic catalyst andfractionally distilling the resulting product. This process isillustrated by the following reaction: ##STR6##

(2) Reacting a 4-alkyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one withdilute aqueous mineral acid and distilling the resulting reactionproduct. This process can be illustrated by the following reaction:##STR7## The photo-oxidation reaction is preferably carried out in aninert solvent such as methanol or a methanol-benzene mixture in thepresence of a reaction sensitizer such as rose bengal and a base such assodium hydroxide and potassium hydroxide. The photo-oxidation is carriedout by bubbling oxygen through the reaction mass. The time of reactionas well as the rate of reaction is a function of the followingvariables:

1. Bubble size of oxygen;

2. Throughput of oxygen per unit of time;

3. Pressure;

4. Concentration of base in reaction mass; and

5. Concentration of UV sensitizer in reaction mass.

Higher pressures give rise to longer oxygen residence time therebypermitting shorter times of reaction and greater yields per unit time.Higher concentrations of reaction sensitizer give rise to fasterreaction rates; up to sensitizer concentrations of 0.5 gm per liter andsensitizer:diene reactant weight ratios of 0.5:4, whereas any furtherincrease in sensitizer concentrations does not give rise to any materialincrease in reaction rate. It is preferable to carry out thephoto-oxidation reaction at a temperature of between 15° C. and 70° C.with room temperature being most convenient.

The second of the above reaction sequences may be carried out using amineral acid, for example dilute aqueous hydrochloric acid, sulfuricacid or phosphoric acid. Preferably the reaction is carried out in thepresence of an inert solvent such as hexane or cyclohexane, at atemperature in the range of from 15° C. up to 70° C., most convenientlyat room temperature.

At the end of each of the foregoing reactions, the reaction mass isdistilled in fractional distillation apparatus yielding the desiredproduct.

Organoleptic properties of materials produced according to theabove-mentioned processes are as follows:

                  TABLE I                                                         ______________________________________                                        Compound     Structure Organoleptic Properties                                ______________________________________                                        2,4,4,6-tetra- methylcyclohexa- 2,5-diene-1-one                                             ##STR8## Flavor: medicinal Fragrance: warm, sweet, slightly                            minty, woody aroma with natural green and hay-like                            nuances Tobacco:Virginia tobacco-like                  4-butyl-3,4,5- trimethyl-2,5- cyclohexadiene-1-one                                          ##STR9## Flavor: sweet, hay-like, heliotropine-like, black                             pepper-like, woody, tobacco-like and "Oriental"                               aroma charac- teristics with sweet, hay- like,                                heliotropine-like, black pepper-like, woody,                                  tobacco, "Oriental"  flavor characteristics                                   Fragrance: sweet, honey-                                                      like celery note with                                                         tobacco and floral nuances                                                    and a distinct Jasmine                                                        undertone                                                                     Tobacco: dry black tobacco                                                    notes as well as pungent,                                                     spicey, celery, black                                                         pepper-like and sweet                                                         notes, both prior to and                                                      on smoking, in the main                                                       stream as well as the                                                         side stream                                            ______________________________________                                    

When the cyclohexadiene derivatives of our invention are used as foodflavor adjuvants, the nature of the co-ingredients included with each ofthe said cyclohexadiene derivatives in formulating the productcomposition will also serve to alter, modify, augment or enhance theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the terms "alter," "modify," and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character, or taste."

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, chewing gums, vegetables, cereals, soft drinks,snacks and the like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber,or certain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the cyclohexadiene derivative(s) of our invention, and inaddition, sweetening agents which may be sugars, including sucrose ordextrose and/or artificial sweeteners such as cyclamates or saccharin.Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenondeleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxytoluene(2,6-di-tertiary-butyl-4-methylphenol), propyl gallate and the like; andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin; proteinaceous materials; lipids;carbohydrates; starches; pectins; and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses;disaccharides,e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myrisitic acid and thelike; mono- and diglycerides of fatty acids; lecithin; defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methylbutyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal,beta, beta-dimethyl-acrolein, methyl-n-amyl ketone, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methylfurfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, eugenol,linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethylnaphthalene, dodecane, methyldiphenyl,methyl-naphthalene, myrcene, naphthalene, octadecane, tetradecane,tetramethylnephthalene, tridecane, trimethylnaphthalene, undecane,caryophyllene, 1-phellandrene, p-cymene, 1-alpha-pinene; pyrazines suchas 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oilssuch as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla, lactones such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, and acetals (e.g.,1,1-diethoxy-ethane, 1,1-dimethoxy-ethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the cyclohexadiene derivative(s)of our invention by not covering or spoiling the organoleptic properties(aroma and/or taste) thereof; (ii) be non-reactive with thecyclohexadiene derivative(s) of our invention, and (iii) be capable ofproviding an environment in which the cyclohexadiene derivative(s) canbe dispersed or admixed to provide a homogeneous medium. In addition,selection of one or more flavoring adjuvants, as well as the quantitiesthereof, will depend upon the precise organoleptic character desired inthe finished product. Thus, in the case of flavoring compositions,ingredient selection will vary in accordance with the foodstuff, chewinggum, medicinal product or toothpaste to which the flavor and/or aromaare to be imparted, modified, altered, or enhanced. Incontradistinction, in the preparation of solid products, e.g., simulatedfoodstuffs, ingredients capable of providing normally solid compositionsshould be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of thecyclohexadiene derivative(s) employed in a particular instance can varyover a relatively wide range, depending upon the desired organolepticeffects to be achieved. Thus, correspondingly greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected be effective, i.e., sufficient to alter, modify orenhance the organoleptic characteristics of the parent composition,whether foodstuff per se, chewing gum per se, medicinal product per se,toothpaste per se, or flavoring composition.

The use of insufficient quantities of the cyclohexadiene derivative(s)will, of course, substantially vitiate any possibility of obtaining thedesired results while excess quantities prove needlessly costly and inextreme cases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of the cyclohexadienederivative(s) ranging from a small but effective amount, e.g., 0.5 partsper million up to about 100 parts per million based on totalcomposition, are suitable. Concentrations in excess of the maximumquantity stated are not normally recommended since they fail to provecommensurate enhancement of organoleptic properties. In those instanceswherein a cyclohexadiene derivative is added to the foodstuff as anintegral component of a flavoring composition, it is, of course,essential that the total quantity of flavoring composition employed besufficient to yield an effective concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the cyclohexadiene derivative(s) inconcentrations from about 0.1% up to about 15% by weight based on thetotal weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the cyclohexadiene derivative(s) with,for example, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form, e.g,a fruit-flavored powder mix, are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and the cyclohexadienederivative(s) in a dry blender until the requisite degree of uniformityis achieved.

It is presently preferred to combine with the cyclohexadienederivative(s) of our invention the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl anthranilate;

5-Methylfurfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

Damascone (1-crotonyl-2,2,6-trimethylcyclohexen-1-one);

Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene);

Beta-cyclohomocitral (2,2,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxy benzene);

Isoelemecine (4-propenyl-1,2,6-trimethoxybenzene);

2-(4-Hydroxy-4-methylpentyl)-norbornadiene prepared according to ExampleII of U.S. Pat. No. 3,911,028 issued on Oct. 7, 1975;

Reaction product of L-proline and4-hydroxy-2,5-dimethyl-2(H)-furan-3-one (as produced according toExample I of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974);

Reaction product of L-proline with4-hydroxy-2,5-dimethyl-2(H)-furan-3-one (produced according to ExampleII of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974);

Reaction product of L-proline with4-hydroxy-2,5-dimethyl-2(H)-furan-3-one (produced according to ExampleIII of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974);

Reaction product of L-proline with4-hydroxy-2,5-dimethyl-2(H)-furan-3-one (produced according to ExampleIV of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974);

Reaction product of ethyl maltol with L-proline (produced according toExample VI of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974);

Reaction product of cyclotene with L-proline (produced according toExample VIII of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974); and

Reaction product of ethyl cyclotene with L-proline (produced accordingto Example IX of U.S. Pat. No. 3,782,973 issued on Jan. 1, 1974).

The cyclohexadiene derivative(s) of our invention and one or moreauxiliary perfume ingredients, including, for example, alcohols,aldehydes, nitriles, esters, cyclic esters and natural essential oils,may be admixed so that the combined odors of the individual componentsproduce a pleasant and desired fragrance, particularly and preferablyhoney and Jasmine fragrances. Such perfume compositions usually contain(a) the main note or the "bouquet" or foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatives which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation and substanceswhich retard evaporation; and (d) topnotes which are usually-lowboiling, fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theoverall sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, one or moreof the cyclohexadiene derivative(s) can be used to alter, modify orenhance the aroma characteristics of a perfume composition, for example,by utilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of cyclohexadiene derivative(s) of our invention which willbe effective in perfume compositions as well as in perfumed articles andcolognes depends on many factors, including the other ingredients, theiramounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.01% of a cyclohexadienederivative(s) or even less (e.g., 0.005%) can be used to impart warm,sweet, slightly minty, woody, natural green, herbaceous, Jasmine-like,fruity aromas to soaps, cosmetics or other products. The amount employedcan range up to 70% of the fragrance components and will depend onconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

The cyclohexadiene derivative(s) of our invention is(are) useful [takenalone or together with other ingredients in perfume compositions] as anolfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations such aslacquers, brilliantines, pomades and shampoos, cosmetic preparationssuch as creams, deodorants, hand lotions and sun screens; powders suchas talcs, dusting powders, face powders and the like. When used as anolfactory component(s), as little as 1% of cyclohexadiene derivative(s)will suffice to impart an intense floral note to honey or Jasmineformulations. Generally no more than 3% of cyclohexadiene derivativebased on the ultimate end product is required in the perfumecomposition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the cyclohexadienederivative(s). The vehicle can be a liquid such as a non-toxic alcohol,a non-toxic glycol, or the like. The carrier can also be an absorbentsolid, such as a gum (e.g., gum arabic) or components for encapsulatingthe composition (such as gelatin).

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor includingmethods of making the same which overcome problems heretoforeencountered in the creation or enhancement of specific desired "dryblack tobacco-like" notes, spicey notes, celery-like notes, blackpepper-like notes, sweet notes and Virginia tobacco-like notes. Thesenotes, both prior to and on smoking, in both the main stream and theside stream, may now be readily controlled and maintained at the desireduniform level regardless of variations in the tobacco components of theblend; or the nature of the filter used in conjunction with the smokingtobacco article.

This invention further provides improved tobacco additives and additivesfor materials used in the fabrication of tobacco articles (particularlysmoking tobacco articles) and methods whereby desirable "dry blacktobacco-like" notes, spicey notes, celery-like notes, black pepper-likenotes, sweet notes and Virginia tobacco-like notes prior to and onsmoking, in both the main stream and the side stream, may be imparted tosmoking tobacco products and may be readily varied and controlled toproduce the desired uniform flavoring characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g., dried lettuce leaves)an aroma and flavor additive containing as an active ingredient, one ormore of the cyclohexadiene derivatives of our invention.

In addition to the cyclohexadiene derivatives of our invention, otherflavoring and aroma additives may be added to the smoking tobaccomaterial or substitute therefor either separately or in mixture with oneor more of the cyclohexadiene derivatives:

I. Synthetic Materials

Beta-methylcinnamaldehyde;

Eugenol;

Dipentene;

Damascenone;

Maltol;

Ethyl maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexen-1-ol;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2-Methyl-5-isopropylacetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-(2,1-b)-furan;

4-Hydroxyhexanoic acid, gamma-lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot oil;

Cocoa extract;

Nutmeg oil;

Origanum oil.

An aroma and flavoring concentrate containing one or more of thecyclohexadiene derivatives of our invention and, if desired, one or moreof the above-indicated additional flavoring additives may be added tothe smoking tobacco material, to the filter or to the leaf or paperwrapper or to a filter which is part of the smoking article. The smokingtobacco material may be shredded, cured, cased and blended tobaccomaterial or reconstituted tobacco material or tobacco substitutes (e.g.,lettuce leaves) or mixtures thereof. The proportions of flavoringadditives may be varied in accordance with taste, but insofar asenhancement or the imparting of "dry black tobacco-like" notes, spiceynotes, celery-like notes, black pepper-like notes, sweet notes andVirginia tobacco-like notes prior to and on smoking, in both the mainstream and the side stream, we have found that satisfactory results areobtained if the proportion by weight of the sum total of cyclohexadienederivative to smoking tobacco material is between 50 ppm and 1500 ppm(0.005%-0.15%) of the active ingredients to the smoking tobaccomaterial. We have further found that satisfactory results are obtainedif the proportions by weight of the sum total of cycloohexadienederivative used to flavoring material is between 0.05:1 and 0.50:1.

Any convenient method for incorporating the cyclohexadiene derivative(s)in the tobacco product may be employed. Thus the cyclohexadienederivative(s) taken alone or along with other flavoring additives may bedissolved in a suitable solvent such as ethanol, pentane, diethyl etherand/or other volatile organic solvents, and the resulting solution mayeither be sprayed on the cured, cased and blended tobacco material; orthe tobacco material or filter may be dipped into such solution. Undercertain circumstances a solution of cyclohexadiene derivative(s) takenalone or taken further together with other flavoring additives as setforth above, may be applied by means of a suitable applicator such as abrush or roller on the paper or leaf wrapper for the smoking product, orit may be applied to the filter by either spraying or dipping orcoating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated, and the thus-treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases the tobacco treated may have one or morecyclohexadiene derivative(s) of our invention in excess of the amountsor concentrations above indicated so that when blended with othertobaccos, the final product will have the percentage within theindicated range.

In accordance with one specific example of our invention an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of a 50:50 mixture of2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one and4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one in an amount to providea tobacco composition containing 600 ppm by weight of2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one and 600 ppm of4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one on a dry basis.Thereafter the alcohol is removed by evaporation, and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette whentreated as indicated has desired and pleasing "dry black tobacco-like,"spicey, celery-like, black pepper-like, sweet and Virginia tobacco-likenotes which are detectable in the main stream and side streams when thecigarette is smoked.

While our invention is particularly useful in the manufacture of smokingtobacco such as cigarette tobacco, cigar tobacco and pipe tobacco, othertobacco products formed from sheeted tobacco dust or fines may also beused. As stated supra, the cyclohexadiene derivative(s) of our inventioncan be incorporated with materials such as filter tip materials, seampaste, packaging materials and the like which are used along with thetobacco to form a product adapted for smoking. Furthermore thecyclohexadiene derivative(s) of our invention can be added to certaintobacco substitutes of natural or synthetic origin (e.g., dried lettuceleaves) and, accordingly, by the term "tobacco" as used throughout thisspecification is meant any composition intended for human consumption,by smoking or otherwise, whether composed of tobacco plant parts orsubstitute materials or both.

It will thus be apparent that the cyclohexadiene derivative(s) of ourinvention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

The following examples serve to illustrate our invention, and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I Preparation of 1,3,5,5-tetramethylcyclohexa-1,3-diene

Reaction: ##STR10##

To a 5-liter flask fitted with stirrer, thermometer, dropping funnel,reflux condenser, drying tube and nitrogen purge is charged 2100 ml (6.3moles) of a 3 m solution of methyl magnesium chloride intetrahydrofuran. The flask and contents are cooled to 0° C., and 730 g(5.3 moles) of isophorone is added at 0°-5° C. over a two-hour period.The mixture is allowed to warm to room temperature and to standovernight. The reaction mixture is poured over a mixture of 2800 g ofice and 370 g of glacial acetic acid. When all the ice has melted, thelayers are separated and the organics are washed twice with 500 ml ofwater. The solvent is removed on a rotary evaporator, and the product istransferred to a 2-liter flask fitted with a condenser and a waterseparator. Benzene (300 ml) and p-toluenesulfonic acid (0.5 g) areadded, and the mixture is refluxed until no additional water isseparated. The product is distilled on a 12" Goodloe column using areflux ratio of 9:1. A total of 494 g of product is obtained (boilingpoint 66°-67° C. at 42 mm Hg) which is predominantly1,3,5,5-tetramethylcyclohexa-1,3-diene.

EXAMPLE II Preparation of 4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one and2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one

Reaction: ##STR11##

A solution of 40 g (0.3 moles) of 1,3,5,5-tetramethylcyclohexa-1,3-diene(prepared as in Example I), 13 g (0.23 moles) of potassium hydroxide,and 0.3 g of Rose Bengal in 600 ml of methanol is placed in a flask andirradiated at a temperature of 25°-28° C. with a 450 watt tungsten photolamp over a period of two hours. A steady stream of oxygen is bubbledthrough the solution during irradiation. At the end of the two-hourirradiation period, analysis of a sample of the reaction mixture by GLC(10'×1/8" 10% Carbowax 20M on Chromasorb W, programmed from 80°-220° C.at 8°/min.) shows that the starting material is completely consumed andtwo products have formed. Both products are trapped from the GLC columnand analyzed. The first (about 20% of the reaction product) is found tobe 2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one (Compound A) andexhibits the following spectral properties:

    ______________________________________                                        NMR (δ) ppm                                                                              Interpretation                                               ______________________________________                                        1.2              (s, 6H)                                                      1.9              (s, 6H)                                                      6.58             (2, 2H)                                                      ______________________________________                                    

Infrared spectrum: 1630 cm⁻¹ (C═O)

Mass Spectral Analysis (m/e): 107, 150 (m), 135, 39, 41, 91.

FIG. 1 is the NMR spectrum for Compound A. FIG. 2 is the IR spectrum forCompound A.

The second (about 80% of the product mixture) is found to be4-hydroxy-2,4,6,6-tetramethylcyclohex-2-en-1-one (Compound B) andexhibits the following spectral properties:

    ______________________________________                                        NMR (δ) ppm                                                                              Interpretation                                               ______________________________________                                        1.16             (s, 3H)                                                      1.28             (s, 3H)                                                      1.44             (s, 3H)                                                      1.81             (d, 3H)                                                      2.02             (s, 2H)                                                      6.41             (d, 1H)                                                      ______________________________________                                    

Infrared spectrum: 1630 cm⁻¹ (C═O)

Mass Spectral Analysis (m/e): 112, 69, 43, 39, 41, 84

FIG. 3 is the NMR spectrum for Compound B. FIG. 4 is the IR spectrum forCompound B.

The reaction mixture is poured into 500 ml of water, and the organicsare extracted with four 100 ml portions of ether. The ether is removedby means of a rotary evaporator, and the two products are separated bymeans of a careful distillation. Compound A is obtained first and has aboiling point of 60° C. at 1.5 mm Hg. Compound B distills second with aboiling point of 100° C. at 1.5 mm Hg.

EXAMPLE III Preparation of2,7,9,9-Tetramethyl-1,4-Dioxaspiro[4,5]dec-6-en-8-one

Reaction: ##STR12##

To a 2-liter flask fitted with a reflux condenser, a water separator anda stirrer is charged 265 g of 2,6,6-trimethylcyclohex-2-en-1,4-dione(prepared by the method described in Helv. Chim. Acta, 39:2041 [1956]),266 g of propylene glycol, 500 ml of benzene and 1 g ofp-toluenesulfonic acid. The reactants are stirred and refluxed until noadditional water is collected in the water separator. The product iswashed with water to a pH of 6, and the solvent is stripped off. Theresidue is vacuum distilled through a 9" Goodloe column to yield 257 gof product, boiling point 92° C. at 1 mm Hg (80% yield).

EXAMPLE IV Preparation of4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one

Reaction: ##STR13##

A solution of 20 g of2,7,9,9-tetramethyl-1,4-dioxaspiro[4,5]dec-6-en-8-one (prepared by themethod of Example III) in hexane is stirred while a solution of n-butyllithium in hexane is added dropwise. When no additional exotherm occurs,the addition is stopped and the mixture is stirred for about 15 minutes.Water is added with stirring to hydrolyze the lithium salt. The organiclayer is separated, and the hexane is allowed to evaporate leaving oilycrystals which are recrystallized from cyclohexane yielding 10 g of4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one, melting point90°-93° C. The compound exhibits the following spectral characteristics:

    ______________________________________                                        NMR (δ) ppm                                                                              Interpretation                                               ______________________________________                                         0.87            (t, 3H)                                                       1.02            (s, 3H)                                                       1.05            (s, 3H)                                                      1.05-2.1         (complex signals, 4H)                                        1.98             (s, 3H)                                                      2.35             (q, 4H)                                                      ______________________________________                                    

Infrared analysis: 1640 cm⁻¹ (C═O)

Mass Spectral Analysis (m/e): 43, 41, 29, 39, 27, 28, 11, 154, 210 (m).

FIG. 5 is the NMR spectrum. FIG. 6 is the IR spectrum.

EXAMPLE V Preparation of 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one

Reaction: ##STR14##

A solution of 7 g of4-butyl-4-hydroxy-3,5,5-trimethyl-2-cyclohexen-1-one (prepared by theprocedure of Example IV) in hexane is stirred overnight with 10 ml of a5% solution of HCl. The hexane is separated and evaporated, and theresidue is distilled through a micro column using triethanolamine as astill base. The product obtained is4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one, boiling point 112°-119°C. at 0.1 mm Hg. The compound exhibits the following spectralcharacteristics:

    ______________________________________                                        NMR (δ) ppm (CdCl.sub.3)                                                                  Interpretation                                              ______________________________________                                        0.85              (t, 3H)                                                     1.26              (s, 3H)                                                     1.0-2.0           (complex signals, 4H)                                       2.00              (s, 6H)                                                     6.10              (s, 2H)                                                     ______________________________________                                    

FIG. 7 is the NMR spectrum

Mass Spectral Analysis (m/e) (order of intensity) 136, 121, 41, 29, 27,91.

EXAMPLE VI

The following mixture is prepared:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Phenylacetic acid   70.0                                                      Coumarin            20.0                                                      Phenylethylphenyl acetate                                                                         100.0                                                     Phenyl ethyl alcohol                                                                              5.0                                                       Benzyl benzoate     100.0                                                     Dimethylphenylethyl carbinol                                                                      10.0                                                      Methyl anthranilate 5.0                                                       Beta ionone         10.0                                                      2,4,4,6-tetramethyl-2,5-cyclohexadien-                                        1-one               30.0                                                      ______________________________________                                    

The 2,4,4,6-tetramethyl-2,5-cyclohexadien-1-one imparts a warm, sweet,slightly minty, woody note to this honey formulation, and it enhancesthe herbaceous character thereof.

EXAMPLE VII

The following mixture is prepared:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Para-cresol         3.0                                                       Methyl N-acetylanthranilate                                                                       20.0                                                      Farnesol            3.0                                                       Nerolidol           20.0                                                      Cis-3-hexenyl benzoate                                                                            30.0                                                      Indol               15.0                                                      Eugenol             35.0                                                      Benzyl alcohol      50.0                                                      Methyl linoleate    100.0                                                     Jasmine lactone     30.0                                                      Dihydro methyl Jasmonate                                                                          20.0                                                      Benzyl acetate      500.0                                                     Cis-Jasmone         40.0                                                      Linalool            200.0                                                     4-butyl-3,4,5-trimethyl-2,5-                                                  cyclohexadien-1-one (prepared                                                 according to the process of                                                   Example V)          50.0                                                      ______________________________________                                    

The 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one imparts a green,herbaceous, floralcy of Jasmine to this Jasmine formulation.

EXAMPLE VIII Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill 100 g of talcumpowder with 0.25 g of 2,4,4,6-tetramethylcyclohexa-2,5-diene-1-oneprepared according to Example II. It has a warm, sweet, slightly minty,woody aroma.

EXAMPLE IX Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Patent No. 3,948,818 issuedon April 6, 1976) with a warm, sweet, slightly minty, woody aroma areprepared containing 0.10%, 0.15% and 0.20% of2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one prepared according toExample II. They are prepared by adding and homogeneously mixing theappropriate quantity of 2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one inthe liquid detergent. The detergents all possess a warm, sweet, slightlyminty, woody aroma, the intensity increasing with greater concentrationsof 2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one.

EXAMPLE X Preparation of a Cologne and Handkerchief Perfume

2,4,4,6-Tetramethylcyclohexa-2,5-diene-1-one prepared according to theprocess of Example II is incorporated in a cologne at a concentration of2.5% in 85% aqueous ethanol; and into a handkerchief perfume at aconcentration of 20% (in 95% aqueous ethanol). A distinct and definitewarm, sweet, slightly minty, woody aroma is imparted to the cologne andto the handkerchief perfume.

EXAMPLE XI Preparation of Soap Composition

One hundred grams of soap chips are mixed with one gram of2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one of Example II until ahomogeneous composition is obtained. The perfumed soap compositionmanifests a warm, sweet, slightly minty, woody aroma.

EXAMPLE XII Preparation of a Detergent Composition

A total of 100 g of a detergent powder (Lysine salt of n-dodecylbenzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818issued on Apr. 6, 1976) is mixed with 0.15 g of the2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one of Example II until asubstantially homogeneous composition is obtained. This composition hasa warm, sweet, slightly minty, woody aroma.

EXAMPLE XIII Preparation of a Cosmetic Powder Composition

A cosmetic powder is prepared by mixing in a ball mill 100 g of talcumpowder with 0.25 g of 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-oneprepared according to Example V. It has a green, herbaceous, floralaroma.

EXAMPLE XIV Perfumed Liquid Detergent

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976) with a green, herbaceous, floral aroma are preparedcontaining 0.10%, 0.15% and 0.20% of4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one prepared according toExample V. They are prepared by adding and homogeneously mixing theappropriate quantity of 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-onein the liquid detergent. The detergents all possess a green, herbaceous,floral aroma, the intensity increasing with greater concentrations of4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one.

EXAMPLE XV Preparation of a Cologne and Handkerchief Perfume

4-Butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one prepared according tothe process of Example V is incorporated in a cologne at a concentrationof 2.5% in 85% aqueous ethanol; and into a handkerchief perfume at aconcentration of 20% (in 95% aqueous ethanol. A distinct and definitegreen, herbaceous, floral aroma is imparted to the cologne and to thehandkerchief perfume.

EXAMPLE XVI Preparation of Soap Composition

One hundred grams of soap chips are mixed with one gram of4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one of Example V until asubstantially homogeneous composition is obtained. The perfumed soapcomposition manifests an excellent green, herbaceous, floral aroma.

EXAMPLE XVII Preparation of a Detergent Composition

A total of 100 g of a detergent powder (Lysine salt of n-dodecylbenzenesulfonic acid as more specifically described in U.S. Pat. No. 3,948,818issued on Apr. 6, 1976) is mixed with 0.15% of the4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one of Example V until asubstantially homogeneous composition is obtained. This composition hasan excellent green, herbaceous, floral aroma.

EXAMPLE XVIII Preparation of a Cologne and Handkerchief Perfume

The composition of Example VI is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use of2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one in the composition ofExample VI affords a distinct and definite strong warm, sweet, slightlyminty, woody aroma with a definite honey-like fragrance having aherbaceous character.

EXAMPLE XIX Preparation of a Cologne and a Handkerchief Perfume

The composition of Example VII is incorporated in a cologne at aconcentration of 2.5% in 85% aqueous ethanol; and into a handkerchiefperfume at a concentration of 20% (in 95% aqueous ethanol). The use of4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one in the composition ofExample VII affords a strong Jasmine aroma with green, herbaceous andfloral notes to the handkerchief perfume and cologne.

EXAMPLE XX

A white bread dough mix is prepared by mixing 1350 g of wheat flour and800 ml water. To the mix is added:

    ______________________________________                                        Ingredient               Amount (grams)                                       ______________________________________                                        Yeast                    27.0                                                 Sodium chloride          27.0                                                 Sucrose                  67.5                                                 Shortening               54                                                   Non-fat dry milk powder  40.5                                                 Yeast food (Arkady; manufactured by                                           Fleischmann, Div. of Standard Brands)                                                                  0.50                                                 Softening agents (succinylated monogly-                                       cerides; manufactured by Kraft Div. of                                        National Dairy Products Corporation)                                                                   3.4                                                  ______________________________________                                    

Twelve grams of the product obtained in Example V,4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one, are added to the dough.The dough is then mixed for 8 minutes and allowed to rise for 45 minutesat 40° C. The dough is then baked for 45 minutes at 210° C.

The breadstuff product obtained has a flavor note reminiscent of thecrust of home-made Italian bread and has acceptable and persistentflavor properties for a period of one week and has good flavorcharacteristics when spread with margarine.

By way of comparison, breadstuffs similarly prepared but omitting thecompound of Example V have a flat taste, show typical flavordeterioration on storage during a period of one week, and require anexpensive butter spread to provide an acceptable flavor.

EXAMPLE XXI

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Bright             40.1                                                       Burley             24.9                                                       Maryland           1.1                                                        Turkish            11.6                                                       Stem (flue cured)  14.2                                                       Glycerine          2.8                                                        Water              5.3                                                        ______________________________________                                    

The above tobacco is used in producing cigarettes, and the followingformulation is compounded and incorporated into each of thesecigarettes.

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Ethyl butyrate     .05                                                        Ethyl valerate     .05                                                        Maltol             2.00                                                       Cocoa extract      26.00                                                      Coffee extract     10.00                                                      Ethyl alcohol      20.00                                                      Water              41.90                                                      ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with 2,4,4,6-tetramethylcyclohexa-2,5-diene-1-oneproduced according to Example II, at 100 ppm per cigarette. Anotherone-third of these model cigarettes are treated in the filter with the2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one produced according toExample II, at the rate of 2×10⁻⁵ gm and 3×10⁻⁵ gm. When evaluated bypaired comparison, the cigarettes treated both in the tobacco and in thefilter with the 2,4,4,6-tetramethylcyclohexa-2,5-diene-1-one are found,in smoke flavor, to be more tobacco-like with enhanced Virginiatobacco-like notes.

EXAMPLE XXII

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Bright             40.1                                                       Burley             24.9                                                       Maryland           1.1                                                        Turkish            11.6                                                       Stem (flue cured)  14.2                                                       Glycerine          2.8                                                        Water              5.3                                                        ______________________________________                                    

The above tobacco is used in producing cigarettes, and the followingformulation is compounded and incorporated into each of thesecigarettes.

    ______________________________________                                        Ingredient         Parts by Weight                                            ______________________________________                                        Ethyl butyrate     .05                                                        Ethyl valerate     .05                                                        Maltol             2.00                                                       Cocoa extract      26.00                                                      Coffee extract     10.00                                                      Ethyl alcohol      20.00                                                      Water              41.90                                                      ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at therate of 0.1%. One-third of these model cigarettes are treated in thetobacco section with 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-oneproduced according to Example V, at 100 ppm per cigarette. Anotherone-third of these model cigarettes is treated in the filter with the4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one produced according toExample V at the rate of 2×10⁻⁵ and 3×10⁻⁵ gm. When evaluated by pairedcomparison, the cigarettes treated both in the tobacco and in the filterwith the 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one are found, insmoke flavor, to be similar to smoking a cigarette having dry blacktobacco. In addition there are present in the aroma and taste on smokingpungent, spicey, celery, black pepper-like and sweet nuances.

EXAMPLE XXIII Vanilla Flavor Formulation

A basic vanilla flavor is prepared by admixing the followingingredients:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Maltol               2                                                        Vanillin             20                                                       Ethyl Vanillin       3                                                        Anisaldehyde (1% in Propylene                                                   Glycol)            1                                                        Heliotropin (10% in Propylene                                                   Glycol)            2                                                        Ethanol (95%)        12                                                       Propylene Glycol     60                                                                            100      TOTAL                                           ______________________________________                                    

The above flavor is divided into two parts. To the first portion 0.1% byweight of 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one is added. Tothe second portion no additional ingredients are added. The two flavorformulations are compared at the rate of 0.05% in water and submitted toa bench panel for evaluations. All of the panel members prefer thevanilla flavor with the additional4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one as having tastecharacteristics reminiscent to the vanilla bean, more woody notes and alonger lasting aftertaste.

EXAMPLE XXIV Tomato Juice Formulation

The following tomato juice formulation is prepared by admixing thefollowing ingredients:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Maltol               2                                                        Vanillin             20                                                       Ethyl Vanillin       3                                                        Anisaldehyde (1% in Propylene                                                   Glycol)            1                                                        Heliotropin (10% in Propylene                                                   Glycol)            2                                                        Ethanol (95%)        12                                                       Propylene Glycol     60                                                                            100      TOTAL                                           ______________________________________                                    

To a canned tomato juice (manufactured by Campbell Soup Company ofCamden, N.J.; ingredients: pure tomato juice, slightly salted) at therate of 2 ppm is added, 4-butyl-3,4,5-trimethyl-2,5-cyclohexadien-1-one,and is evaluated by a bench panel. The panel concludes that the spiceynotes are increased, with more black pepper notes dded both in aroma andtaste, the aftertaste being fuller and pleasantly longer lasting.

What is claimed is:
 1. A cyclohexadiene derivative having the structure:##STR15##